Cationic polymerization process and catalyst system therefor

ABSTRACT

A process for producing a copolymer of an isoolefin and at least one other comonomer comprising the step of polymerizing a reaction mixture comprising an isoolefin, a catalyst and at least one of a cycloconjugated muitiolefin and an unconjugated cyclic olefin in the presence of an activator comprising a carbo cation producing species, a silica cation producing species and mixtures thereof. The process can be practiced using a slurry polymerization approach. One of the main benefits achieved with the present invention is the conversion of the monomers over a shorter period of time and higher percent conversion than when the activator is not used.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an improved cationic polymerisationprocess and a catalyst system therefor.

2. Description of the Prior Art

Polymers and copolymers of isobutylene are well known in the art. Inparticular, copolymers of isobutylene with conjugated muitiolefin havefound wide acceptance in the rubber field. These polymers are generallytermed in the art butyl rubber. The preparation of butyl rubber isdescribed in U.S. Pat. No. 2.356,128 (Thomas et al.), the contents ofwhich are incorporated herein by reference.

The term butyl rubber as used throughout this specification is intendedto encompass copolymers made from the polymerization of a reactionmixture comprising an isoolefin having from 4 to 7 carbon atoms (e.g.,isobutylene) and a conjugated multiolefin having from 4 to 14 carbonatoms (e.g., isoprene). Although these copolymers arc said to containabout 0.2 to about 15% combined multiolefin, in practice the butylrubber polymers of commerce contain from about 0.6 to about 4.5 wt % ofmultiolefin; more specifically from about 0.1 to about 2 mole %, theremainder of the polymer being comprised of the isoolefin component.

Efforts to prepare isoolefin-multiolefin polymers of higher unsaturationhave met with varying degrees of success. Where substantially gel-freepolymers have been prepared containing more than about 5% multiolefin,the polymers have been of low number average molecular weight. This hasbeen true even where these polymers had high viscosity average molecularweights. In general, however, the products formed by prior art processeseither high in gel content or low in number average molecular weight areof little utility. In order to have practical commercial utility as asynthetic butyl rubber, the isobutylene-isoprene copolymers must besubstantially gel-free and have a number average molecular weight of atleast 120,000.

The problem associated with the relatively low unsaturation content ofconventional butyl rubber is the correspondingly low number ofcrosslinking sites which can bond with another rubber. Also, thecrosslinking behaviour of conventional butyl rubber is different thanthat of other highly unsaturated rubber. These properties ofconventional butyl rubber result in a weak adhesive strength which isfurther decreased when exposed to external shock, vibration and thelike.

Thus, isobutene-cyclopentadicnc copolymer has been proposed in the priorart as an alternative to conventional butyl rubber.Isobutene-cyclopentadiene copolymer has an improved adhesive strength aswell as excellent gas barrier properties, even at high degrees ofunsaturation. Further, while the unsaturation of the cyclopentadienemoiety in the copolymer is susceptible to attack by ozone and the like,since the unsaturation is pendant to the polymer backbone (i.e., it doesnot form part of the polymer backbone), the polymer backbone remainssubstantially unaffected. Thus, the aging properties of a vulcanizatemade from the copolymer arc excellent and its improved othercharacteristics make it highly desirable for use in tires.

The general problem with prior art isobutene-cyclopentadiene copolymersis in the production thereof; particularly in commercial quantities. Thespecific problems include one or both of the following:

(i) maintaining the stability of the cyclopentadiene co-monomer for aperiod sufficient to effect co-polymerization (the co-monomer isnormally unstable against heat);

(ii) as the degree of unsaturation increases, there is an increase ingel formation and a decrease in the molecular weight (Mw) of thecopolymer.

The latter problem can be addressed by using a conventional solutionpolymerization approach. See, for example, one or more of:

U.S. Pat. No. 3,808,177 (Thaler et al.);

U.S. Pat. No. 3,856,763 (Thaler et al.)

U.S. Pat. No. 4,031,300 (Thaler et al.); and

U.S. Pat. No. 4,139,695 (Thaler et al.); the contents of which arehereby incorporated by reference.

The use of a solution polymerization approach to produce anisobutene-cyclopentadiene copolymer has been criticized in InternationalPublication Number WO 97/05181 (Youn el al.), the contents of which arehereby incorporated by reference—see, for example, page 3, line 2 topage 4, line 20 of Youn et al. Indeed, the purported point of noveltytaught by Youn et al. relates to a slurry polymerization approach.

Notwithstanding the prior art solution and slurry polymerizationapproaches for the production of isobutene-cyclopentadiene copolymers,there is still room for improvement. Specifically, it would be desirableto have a polymerization process for the production of anisobutene-cyclopentadiene copolymer which could be used with a slurryapproach to produce a low (or negligible) gel content copolymer atrelatively high conversion rates of the cyclopentadiene comonomer in ashortened period of time, thus improving catalyst efficiency which islow compared to state of the art butyl polymerizations.

SUMMARY OF THE INVENTION

It is an object of the present invention to obviate or mitigate at leastone of the above-identified disadvantages of the prior art.

It is another object of the present invention to provide an improvedcatalyst system for isoolefin copolymerization and terpolymerization.

It is another object of the present invention to provide an improvedprocess for isoolefin copolymerization and terpolymerization.

Accordingly, in one its aspects, the present invention provides a slurryprocess for producing a copolymer of an isoolefin and at least one othercomonomer comprising the step of polymerizing a reaction mixturecomprising an isoolefin a catalyst and at least one of a cycloconjugatedmultiolefin and an unconjugated cyclic olefin in the presence of anactivator comprising a carbo cation producing species, a silica cationproducing species and mixtures thereof.

Thus, the present inventors have surprisingly and unexpectedlydiscovered that the use of a specific activator in this cationicpolymerization process surprisingly and unexpectedly improves theprocess by exhibiting an improved conversion in less time whilemaintaining a desirable Mw. This is indeed surprising given theteachings of Kennedy et al. (J. Macromol. Sci. Chem. A1(6). p. 977-993(1967), the contents of which are hereby incorporated by reference)wherein tert-butyl chloride was used as chain transfer agent andresulted in a decrease of Mw. The present process is characterized bylack of a significant decrease of Mw, especially when the process isconducted in semi-batch mode.

One of the main benefits achieved with the present invention is theconversion of the monomers over a shorter period of time and higherpercent conversion than when the activator is not used. Further, one ormore of the following advantages may also accrue:

1. high conversion of a second comonomer in a shortened period of time;

2. a low or negligible gel content;

3. the ability to achieve useful results at temperatures in the range offrom about −110° C. to about −80° C.;

Other advantages will be apparent to those of skill in the art.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention relates to a method of preparing a copolymer of anisoolefin and at least one of a cycloconjugated multiolefin and anunconjugated cyclic olefin. Of course, those of skill in the art willrecognize that the products of the present process may be at least anyone of: a copolymer of an isoolefin and a cycloconjugated multiolefin; acopolymer of an isoolefin and an unconjugated cyclic olefin; aterpolymer of an isoolefin, a cycloconjugated multiolefin and anunconjugated cyclic olefin; a terpolymer of an isoolefin and two (ormore) different cycloconjugated multiolefins; and a terpolymer of anisoolefin and two (or more) different unconjugated cyclic olefins.

Preferably, the copolymer has a number average molecular weight about30,000 to about 600,000, more preferably about 50,000 to about 400,000,still more preferably about 70,000 to about 350,000 and a mole %unsaturation of at least about 1 to about 45 mole %, more preferably atleast about 1 to about 40 mole %, and most preferably the unsaturationis about 2-25%.

Preferably, the isoolefin suitable for use in the present process is aC₄-C₁₀ hydrocarbon monomer. Non-limiting examples of suitable isoolefinmay be selected from the group comprising isobutylene,2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene and mixturesthereof. The preferred isoolefin is isobutylene.

Preferably, the cycloconjugated multiolefin suitable for use in thepresent process is a C₅-C₂₀ hydrocarbon monomer having at least one pairof conjugated double bonds. The monomer may comprise a 5-membered ringstructure. Non-limiting examples of suitable monomers including such aring structure may be selected from the group comprisingcyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene,1,3-dimethylcyclopentadiene and mixtures thereof. Further, the monomermay comprise a 6-membered ring structure comprising a conjugated diene.Non-limiting examples of suitable monomers including such a ringstructure may be selected from the group comprising 1,3-cyclohexadiene,1-methyl-1,3-cyclohexadiene, 1-methylene-2-cyclohexene,2-methyl-1,3-cyclohexadiene, 1,3-dimethyl-1,3-cyclohexadiene andmixtures thereof.

Indene and its derivatives may also be used.

Preferably, the unconjugated cyclic olefin suitable for use in thepresent process is a bicyclic containing an unsaturated bond.Non-limiting examples of suitable such monomers may be selected from theterpenes—e.g., β-pinene.

In a preferred embodiment, terpolymers of an isobutylene, acyclo-conjugated diolefin and a third monomer (e.g., unconjugatedterpenes) can be prepared according to the method embodied by thepresent process wherein these terpolymers have a number averagemolecular weight (Mn) of about 30,000 to about 600,000, more preferablyabout 50,000 to about 400,000 and stiff more preferably about 70,000 toabout 350,000; and a mole % unsaturation of cyclopentadiene at least 1to about 45 mole %, more preferably at least 1 to about 25 mole Thetotal unsaturation from all comonomers and cyclopentadiene is preferablybetween 1 and 45 mole %, more preferably between 1 and 40 mole %, andmost preferably between 1 and 30 mole %.

It is possible and preferred to practice the present process using aslurry polymerization approach. As is known in the art, the use of aslurry polymerization allows for higher conversions than for solutionpolymerization (e.g., 90% to 95% or more) without a concurrent increasein viscosity in the reaction mixture.

The slurry polymerization approach utilizes a diluent which is anon-solvent for the polymer product. The choice of diluent is within thepurview of those of skill in the art. Preferably, the diluent is a polardiluent. The term polar diluent as used in the specification and claims,means liquids having a dielectric constant at 25° C. of less than about20, more preferably less than about 17, most preferably less than about10. These liquids however, preferably do not contain sulfur, oxygen orphosphorus in the molecule since compounds containing these elementswill react with or otherwise deactivate the catalyst.

The preferred polar diluents are inert halogenated aliphatichydrocarbons, more preferably halogenated paraffinic hydrocarbons andvinyl or vinyl idene halides, most preferably primary or secondarychlorinated paraffinic hydrocarbons. The term inert means that thecosolvent will not react with the catalyst or otherwise enter into thepolymerization reaction. The halogenated hydrocarbon is preferably aC₁-C₅ paraffinic hydrocarbon, more preferably a C₁-C₂, paraffin. Theratio of carbon atoms to halogen atoms in the polar diluent ispreferably 5 or less. Preferably the halogen is chlorine.

Illustrative examples of these polar diluents are methylchloride, ethylchloride, propyl chloride, methyl bromide, ethyl bromide, chloroform,methylene chloride, vinyl chloride, vinylidine chloride,dichloroethylene, etc. Preferably, the polar diluent is methyl chlorideor ethyl chloride.

When using the slurry polymerization approach, any of the catalystsdiscussed above with respect to the solution polymerization approach maybe used

In the practice of this invention, a catalyst is used. Preferably, inthe slurry polymerization approach, the catalyst has the formula AlY₃wherein Y is a halogen. The most preferred catalyst for use in theslurry approach is AlCl₃. However, the use of aluminum catalysts inZiegler-Natta polymerization process is well known and alternativechoices of aluminum catalyst to he used in the present process arewithin the purview of a person skilled in the art. For example, thealuminum catalyst may comprise at least one compound having the formula:

 (R)_(p)AlY_(q)

wherein R is selected from the group comprising a C₂-C₁₀ alkyl group, aC₂-C₁₀ alkoxyl group and a C₃-C₂₀ cycloalkyl group, Y is a halogen andp+q is 3. More preferably, q is not 0. Possibly, the aluminum catalystcomprises a mixture of at least two of said compounds.

Preferably, p is a number in the range of from about 1 to about 2, and qis a number in the range of from about 1 to about 2. In a more preferredembodiment, p is 2 and q is 1. In another more preferred embodiment, pand q are 1.5. In yet another more preferred embodiment, p is 1 and q is2.

Preferably, R is ethyl.

Of course, the halogen Y in the preferred formula for the aluminumcatalyst may he selected from the group comprising bromide, chloride,iodide and astatine. The preferred halogen moiety is chloride. If two ormore halogen moieties are present on the aluminum catalyst, it ispreferred that they be the same.

Non-limiting examples of aluminum catalysts useful in the presentinvention may be selected from the group comprising diethyl aluminumchloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride,methyl diethoxy aluminum, methylalumninum dichloride, isobutylaluminumdichloride, methylalumninum dibromide, ethylaluminum dibromide,benzylaluminum dichloride, phenylaluminum dichioride; xylylaluminumdichloride, toluylaluminum dichloride, butylaluminum dichloride,hexylaluminum dichloride, octylaluminum dichloride, cyclohexylaluminumdichloride and mixtures thereof. The preferred catalysts aremethylaluminum dichloride, ethylaluminum dichloride, isobutylaluminumdichloride, dimethylaluminum chloride, diethylaluminum chloride,diisobutylaluminum chloride and mixtures thereof. As is known to thoseof skill in the art, if it is desired to utilize ethyl aluminumsesquichloride as the aluminum catalyst, it is possible to produce thecocatalyst by mixing equimolar amounts of diethyl aluminum chloride andethyl aluminum dichloride.

Where an aluminum halide is used, it is preferably in the form of anhomogeneous solution or submicron dispersion of catalyst particles,e.g., colloidal dispersion. Therefore, the catalyst is preferablydispersed or dissolved in a suitable catalyst solvent or mixtures ofsolvents. The catalyst solvent preferably is a polar solvent.

It is preferred the aluminum halide catalyst be in solution in the polarorganic solvent prior to introduction of the catalyst to the reactionmedium.

Use of the term solution with reference to the polar organicsolvent/aluminum halide systems is intended to include both truesolution and colloidal dispersions since they may exist concurrently inthe same system.

The aluminum halide/polar solvent catalyst preferably comprises about0.01 to about 2 wt. % aluminum halide, more preferably about 0.01 toabout 1, most preferably 0.04 to about 0.8.

The hydrocarbylaluminum dilialide catalyst may be added neat or insolution. Preferably where a catalyst solvent is used, it is a liquidparaffin solvent or cycloparaffin solvent. It is advantageous though notnecessary to use paraffins of low freezing point. Methylcyclohexanc isparticularly useful since catalyst solutions of about 1% concentrationdo not freeze at −120° C.

The concentration of the catalyst is not critical. Very dilute catalystsolutions, however, are not desirable since substantial fractions of thecatalyst may be deactivated by impurities. Very concentrated solutionsare undesirable since at polymerization temperatures catalyst may belost by freezing out of solution.

In carrying out the present process, those skilled in the art will beaware that only catalytic amounts of catalyst solution are required.Preferably, the volume ratio of monomer plus diluent to catalystsolution is about 100/1 to about 9/1, more preferably about 80/1 toabout 10/1, most preferably about 50/1 to about 20/1.

It is desirable to conduct the reaction below about −80C, morepreferably about 90C to 110C.

Specifically preferred embodiments of this slurry approach will beillustrated in the Examples hereinbelow. For more general information,see, for example, Youn et al., referred to and incorporated by referencehereinabove.

In the present process, use is made of an activator comprising a carbocation producing species, a silica cation producing species and mixturesthereof.

Preferably, the activator is used in an amount in the range of fromabout 0.0005 to about 0.2, more preferably from about 0.001 to about0.1, most preferably from about 0.002 to about 0.06, weight % based onthe total weight of the monomers.

In one preferred embodiment, the activator is a carbon cation producingspecies having the formula:

 R¹—X

wherein R¹ is a C₁-C₄₀ hydrocarbon, optionally substituted with one ormore heteroatoms, and X is selected from the group comprising a halogen,—OH and —OR², wherein R² is the same or different as R¹ and is a C₁-C₄₀hydrocarbon, optionally substituted with one or more heteroatoms. In onepreferred embodiment, each of R¹ and R² is a C₁-C₄₀ straight chain orbranched alkyl group, optionally having one or more unsaturations. Inanother preferred embodiment, each of R¹ and R² is a substituted orunsubstituted C₅-C₄₀ aryl group. In yet another embodiment, each of R¹and R² is a substituted or unsubstituted C₃-C₄₀ cycloalkyl group.Preferably, X is selected from the group comprising Cl, Br and I.

The more preferred embodiments of X may be selected from the groupcomprising Cl, OH and OCH₃.

In another preferred embodiment, the activator has the formula:

X¹—R—X²

wherein R is a C₁-C₄₀ hydrocarbon, optionally substituted with one ormore heteroatoms, and X¹ and X² are the same or different and each is ahalogen, —OH and —OR³, wherein R³ is a C₁-C₄₀ hydrocarbon, optionallysubstituted with one or more heteroatoms.

In one preferred embodiment, R is a C₁-C₄₀ straight chain or branchedalkyl group, optionally having one or more unsaturations. In anotherpreferred embodiment, R is substituted or unsubstituted C₅-C₄₀ arylgroup. In yet another preferred embodiment, R is a substituted orunsubstituted C₃-C₄₀ cycloalkyl group.

In one preferred embodiment, R³ is a C₁-C₄₀ straight chain or branchedalkyl group, optionally having one or more unsaturations. In anotherpreferred embodiment, R³ is a substituted or unsubstituted C₅-C₄₀ arylgroup. In yet another preferred embodiment, R³ is a substituted orunsubstituted C₃-C₄₀ cycloalkyl group.

Preferably, X¹ and X² are selected from the group comprising Cl, Br andI, more preferably both X¹ and X² are Cl.

Non-limiting examples of activators which are useful in the presentprocess as suitable carbo cation producing species include:

wherein R is C₁-C₄₀ hydrocarbon, optionally substituted with one or moreheteroatoms,

and cis and trans isomers of

CH₂C—CH═CH—CH₂Cl

In another preferred embodiment, the activator may be selected from thegroup comprising allyl chloride, tert-butylehloride, benzyl chloride,4-methylbenzyl chloride and mixtures thereof.

In another preferred embodiment, the activator is a silica cationproducing species having the formula:

R⁴R⁵R⁶SiX

wherein R⁴, R⁵ and R⁶ are the same or difference and each is a C₁-C₄₀hydrocarbon, optionally substitute d with one or more peteroatoms and Xa halogen. In one preferred embodiment, each of R⁴, R⁵ and R⁶ is aC₁-C₄₀ straight chain or branched alkyl group, optionally having one ormore unsaturations. In another preferred embodiment, each of R⁴, R⁵ andR⁶ is a substituted or unsubstituted C₅-C₄₀ aryl group. In yet anotherpreferred embodiment, each of R⁴, R⁵ and R⁶ is a substituted orunsubstituted C₅-C₄₀ cycloalkyl group. Preferably, X is selected fromthe group comprising Cl, Br and I, more preferably X is Cl. A preferrednon-limiting example of a silica cation producing species is trimethylsilyl halide.

Embodiments of the present invention will now be described withreference to the following Examples which should not be construed aslimiting the scope of the invention.

EXAMPLE 1

At −30° C., 0.0267 g AlCl₃ (purity 99.99% <100 ppm H₂O) was dissolved in55.4 mL methylchloride (<20 ppm H₂O) to form a catalyst solution. Thesolution was stirred for 30 minutes at −30° C. and then cooled down to−95° C.

In a 500 mL 3-necked reaction flask equipped with an overhead stirrer, areaction mixture consisting of 0.66 g cyclopentadiene, 38.5 mL isobuteneand 161 mL methylchloride was stirred at −95° C. The temperature of themixture was brought to −93° C. and the catalyst solution was added atonce to start the polymerization. All temperature changes during thereaction are followed by a thermocouple.

After 20 minutes, the reaction was stopped by addition to the reactionmixture of 3 mL of a solution of NaOH in ethanol (1.0 wt. %).

The polymerization was carried out in a Braun dry box under dry nitrogenatmosphere (<5 ppm H₂O, <20 ppm O₂).

Solvent, unreacted monomers and ethanol were removed under vacuum andthe polymer yield was determined by gravimetry to be 16.3 wt. %.

By dissolving in hexane and reprecipitation from ethanol, the polymerwas cleaned. After 3 days of drying in a vacuum oven at roomtemperature.the molecular weight, determined by GPC (UV-detection), wasMn=130000; Mw=195000, the cyclopentadiene content in the polymer wasdetermined to 7.2 mol % by ¹H-NMR.

This Example represents a control reaction without addition of anaccelerator, and thus is provided for comparative purposes only.

EXAMPLE 2

The methodology of Example 1 was repeated except that the reactionmixture consisted of 1.65 g cyclopentadiene, 37 mL isobutene and 161 mL,methylchloride. The polymer yield was 13.9 wt. %, the molecular weightif Mn=53000; Mw=130000 and the cyclopentadiene content in the polymerwas 17.9 mol %. This Example represents a control reaction withoutaddition of an accelerator, and thus is provided for comparativepurposes only.

EXAMPLE 3

The methodology of Example 1 was repeated except that the reactionmixture consisted of 0.81 g methylcyclopentadiene, 38.5 mL isobutene and161 mL methylchloride. The polymer a yield was 49.0 wt. %, the molecularweight is Mn=57000; Mw=327000 and the methylcyclopentadiene content inthe polymer was 4.0 mol %. This Example represents a control reactionwithout addition of an accelerator, and thus is provided for comparativepurposes only.

EXAMPLE 4

The methodology of Example 1 was repeated except that the reactionconsisted of 0.33 g cyclopentadiene, 0.40 g methylcyclopentadiene, 38.5mL isobutene and 161 mL methylchloride. The polymer yield was 25.8 wt.%, the molecular weight was Mn=52000; Mw=182000, the cyclopentadienecontent in the polymer was 2.8 mol % and the methylcyclopentadienecontent in the polymer was 3.5 mol %. This Example represents a controlreaction without addition of an accelerator, and thus is provided forcomparative purposes only.

EXAMPLE 5

The methodology of Example 1 was repeated except that 9.3 mgtert-butylchloride were added to the reaction mixture before startingthe reaction. The polymer yield was 77.4 wt. %, the molecular weight wasMn 47000; Mw=109000 and the cyclopentadiene content in the polymer was2.9 mol %.

EXAMPLE 6

The methodology of Example 5 was repeated except that 18.6 mgtert-butylchloride was added to the reaction mixture before starting thereaction. The polymer yield was 98.5 wt. %, the molecular weight wasMn=37000; Mw=75000 and the cyclopentadiene content in the polymer was1.9 mol %.

EXAMPLE 7

The methodology of Example 5 was repeated except that 4.6 mgtert-butylchloride was added to the reaction mixture before starting thereaction. The polymer yield was 50.3 wt. %, the molecular weight wasMn=69000; Mw=134000 and the cyclopentadiene content in the polymer was3.7 mol %.

EXAMPLE 8

The methodology of Example 3 was repeated except that 9.3 mgtert-butylchloride was added to the reaction mixture before starting thereaction. The polymer yield was 70.5 wt. %, the molecular weight wasMn=65000; Mw=310000 and the methylcyclopentadiene content in the polymerwas 2.6 mol %.

EXAMPLE 9

The methodology of Example 4 was repeated except that 9.3 mgtert-butylchloride was added to the reaction mixture before starting thereaction. The polymer yield was 53.1 wt. %, the molecular weight wasMn=32000; Mw=120000. The cyclopentadiene content in the polymer was 1.8mol % and the methylcyclopentadiene content in the polymer was 2.1 mol%.

EXAMPLE 10

The methodology of Example 5 was repeated except that 12.7 mgbenzylchloride was added to the reaction mixture before starting thereaction. The polymer yield was 27.0 wt. %, the molecular weight wasMn=91000: Mw=176000 and the cyclopentadiene content in the polymer was5.6 mol %.

EXAMPLE 11

The methodology of Example 5 was repeated except that 14.1 mg4-methylbenzylchloride was added to the reaction mixture before startingthe reaction. The polymer yield was 20.2 wt. %, the molecular weight wasMn=115000; Mw=185000 and the cyclopentadiene content in the polymer was6.2 mol %.

EXAMPLE 12

The methodology of Example 5 was repeated except that 6.2 mgcis-1,4-dichloro-2-butene was added to the reaction mixture beforestarting the reaction. The polymer yield was 52.9 wt. %, the molecularweight was Mn=72000; Mw=263000 and the cyclopentadiene content in thepolymer was 2.8 mol %.

EXAMPLE 13

The methodology of Example 5 was repeated except that 6.2 mgtrans-1,4-dichloro-2-butene was added to the reaction mixture beforestarting the reaction. The polymer yield was 100 wt. %, the molecularweight was Mn=193000; Mw=1429000 and the cyclopentadiene content in thepolymer was 2.0 mol %.

EXAMPLE 14

The methodology of Example 5 was repeated except that 15.1 mg4-vinylbenzylchloride was added to the reaction mixture before startingthe reaction. The polymer yield was 86.7 wt. %, the molecular weight wasMn=62000; Mw=140000 and the cyclopentadiene content in the polymer was2.3 mol %.

EXAMPLE 15

The methodology of Example 5 was repeated except that 15.1 mgα,α′-dichloro-pxylene was added to the reaction mixture before startingthe reaction. The polymer yield was 99.5 wt. %, to the molecular weightwas Mn=84000; Mw=202000 and the cyclopentadiene content in the polymerwas 2.1 mol %.

EXAMPLE 16

The methodology of Example 5 was repeated except that 9.7 mgα,α,α′,α′-tetramethyl-1,4-benzenedimethanol was added to the reactionmixture before starting the reaction. The polymer yield was 25.4 wt. %,the molecular weight was Mn=87000; Mw=215000 and the cyclopentadienecontent in the polymer was 6.0 mol %.

EXAMPLE 17

At −30° C., 0.0267 g AlCl₃ (purity 99.99%, <100 ppm H₂O) were dissolvedin 55.4 mL methylchloride (<20 ppm H₂O) to form the catalyst solution.The solution was stirred for 30 minutes at −30° C. and then cooleddowned to −95° C.

In a 500 mL 4-necked reaction flask equipped with an overhead stirrerand two jacketed addition funnels, 150 mL of methylchloride was stirredat −93° C. After cooling down the addition funnels to −93° C., one wasfilled with 50 mL of the catalyst solution and the other was filled with50 mL of a reaction solution consisting of 0.66 g cyclopentadiene, 38.5mL isobutene and 11 mL methylchloride. The catalyst and reactionsolutions were added to the reaction flask at a constant rate of 1.4ml/min. All temperature changes during the reaction were followed with athermocouple.

One minute after complete addition of the catalyst and reactionsolutions, the reaction was slopped by adding 3 mL of a solution of NaOHin ethanol (1.0 wt. %) to the reaction mixture.

The polymerization was carried out in a Braun™ dry box under drynitrogen atmosphere (<5 ppm H₂O, <20 ppm O₂).

Solvent, unreacted monomers and ethanol were removed under vacuum andthe polymer yield was determined by gravimetry to 12.3 wt. %.

By dissolving in hexane and reprecipitation from ethanol, the polymerwas cleaned. After 3 days of drying in a vacuum oven at roomtemperature, the molecular weight, determined by GPC (Rl-detection), wasMn=101000; Mw=184000 and the cyclopentadiene content, determined by¹H-NMR spectroscopy, in the polymer was 7.3 mol. %.

This Example represents the semicontinuous control reaction withoutaddition of an accelerator, and thus is provided for comparativepurposes only.

EXAMPLE 18

The methodology of Example 17 was repeated except that the reactionmixture consisted of 0.66 g cyclopentadiene, 38.5 mL isobutene, 9.3 mgtert-butylchloride and 11 mL methylchloride. The polymer yield was 73.6wt. %, the molecular weight was Mn=75000; Mw=210000; and thecyclopentadiene content in the polymer was 2.5 mol-%.

EXAMPLE 19

The methodology of Example 17 was repeated except that the reactionmixture consisted of 0.33 g cyclopentadiene, 0.40 gmethylcyclopentadiene, 38.5 mL isobutene and 11 mL methylchloride. Thepolymer yield was 26.5 wt %, the molecular weight was Mn=94000;Mw=198000; the cyclopentadiene content in the polymer was 2.6 mol-% andthe methylcyclopentadiene content was 5.8 mol-%.

This Example represents the semicontinuous control reaction withoutaddition of an accelerator, and thus is provided for comparativepurposes only.

EXAMPLE 20

The methodology of Example 17 was repeated except that the reactionmixture consisted of 0.33 g cyclopentadiene, 0.40 gmethylcyclopentadiene, 38.5 mL isobutene, 9.3 mg tert-butylchloride and11 mL methylchloride. The polymer yield was 61.1 wt. %, the molecularweight was Mn=98000; Mw=205000; the cyclopentadiene content in thepolymer was 1.3 mol-% and the methylcyclopentadiene content was 2.8mol-%.

EXAMPLE 21

The methodology of Example 17 was repeated except that the reactionmixture consisted of 0.81 g methylcyclopentadiene, 38.5 mL isobutene and11 mL methylchloride. The polymer yield was 26.7 wt. %, the molecularweight was Mn=151000; Mw=397000; and the methylcyclopentadiene contentwas 5.7 mol-%.

This Example represents the semicontinuous control reaction withoutaddition of an accelerator, and thus is provided for comparativepurposes only.

EXAMPLE 22

The methodology of Example 17 was repeated except that the reactionmixture consisted of 0.81 g methylcyclopentadiene, 38.5 mL isobutene,9.3 mg tert-butylchloride and 11 mL methylchloride. The polymer yieldwas 56.3 wt. %, the molecular weight was Mn=135000; Mw365000; and themethylcyclopentadiene content was 2.8 mol-%.

In each of the foregoing Examples, the weight ratio of solvent tomonomers was 8.4, the wt. % of the catalyst solution was 0.047, theweight ratio of the catalyst solution to the monomers was 1.96, thereaction temperature was −93° C. and the reaction time was 20 minutes inExamples 1-16 and 36 minutes in Examples 17-22. Various other parametersof the process of the foregoing Examples and various properties of thepolymers produced in the Examples are provided in the attached tables(Note: PDI=polydispersity index). The results reported in the attachedtables, illustrate advantages of the present process. Specifically,higher polymer yields and catalyst efficiencies are achieved using theaccelerator (i.e., the activator) of the present process when comparedto not using it. This is especially seen in Examples 17-22 where thereis a lack of a significant decrease of Mw for Examples 18, 20 and 22compared to Examples 17, 19 and 21, respectively.

While the invention has been described hereinabove with reference tovarious preferred embodiments and specific Examples, it will be clearlyunderstood by those of skill in the art that modifications to andvariations of the preferred embodiments and specific Examples arepossible which do not depart from the spirit and scope of the presentinvention. Accordingly, it is contemplated that such modifications toand variations of the preferred embodiments and specific Examples areencompassed by the invention.

Wt. % IB in Wt. % CP in Wt. % MeCP in wt.-% accelerator Example Reactionmonomer feed monomer fed Monomer feed in monomer feed Type ofaccelerator 1 Batch 97.6 2.4 0 0 none 2 Batch 94.2 5.8 0 0 none 3 Batch97.2 0 2.8 0 none 4 Batch 97.5 1.1 1.4 0 none 5 Batch 97.6 2.4 0 0.032tert-butylchloride 6 Batch 97.6 2.4 0 0.065 tert-butylchloride 7 Batch97.6 2.4 0 0.016 tert-butylchloride 8 Batch 97.2 0 2.8 0.032tert-butylchloride 9 Batch 97.5 1.1 1.4 0.032 tert-butylchloride 10Batch 97.6 2.4 0 0.044 benzylchloride 11 Batch 97.6 2.4 0 0.0494-methylbenzylchloride 12 Batch 97.6 2.4 0 0.022cis-1,4-dichloro-2-butene 13 Batch 97.6 2.4 0 0.022trans-1,4-dichloro-2-butene 14 Batch 97.6 2.4 0 0.0534-vinylbenzylchloride 15 Batch 97.6 2.4 0 0.031 α,α′-dichloro-p-xylene16 Batch 97.6 2.4 0 0.035 α,α,α′,α′-tetramethyl-1,4-benzenedimethanol 17Semi 97.6 2.4 0 0 none 18 Semi 97.6 2.4 0 0.032 tert-butylchloride 19Semi 97.5 1.1 1.4 0 none 20 Semi 97.5 1.1 1.4 0.032 tert-butylchloride21 Semi 97.2 0 2.8 0 none 22 Semi 97.2 0 2.8 0.032 tert-butylchloride

Yield Catalyst efficiency Mol % CP in Mol % MeCP in Gel Example (%) (kgpolymer/g cat) Mw PDI polymer polymer content 1 16.3 0.17 195000 1.5 7.20.0 not visible 2 13.9 0.15 130000 2.5 17.9 0.0 not visible 3 49.0 0.52327000 5.7 0.0 4.0 not visible 4 25.8 0.28 182000 3.5 2.8 3.5 notvisible 5 77.4 0.82 109000 2.3 2.9 0.0 not visible 6 98.5 1.07 75000 2.01.9 0.0 not visible 7 50.3 0.54 134000 1.9 3.7 0.0 not visible 8 70.50.76 310000 4.8 0.0 2.6 not visible 9 53.1 0.57 120000 3.8 1.8 2.1 notvisible 10 27.0 0.29 176000 1.9 5.6 0.0 not visible 11 20.2 0.22 1850001.6 6.2 0.0 not visible 12 52.9 0.56 263000 3.7 2.8 0.0 not visible 13100.0 1.07 1429000 7.4 2.0 0.0 not visible 14 86.7 0.92 140000 2.3 2.30.0 not visible 15 99.5 1.05 202000 2.4 2.1 0.0 not visible 16 25.4 0.27215000 2.5 6.0 0.0 not visible 17 12.3 0.13 184000 1.8 7.3 0.0 notvisible 18 73.6 0.78 210000 2.8 2.5 0.0 not visible 19 26.5 0.28 1980002.1 2.6 5.8 not visible 20 61.1 0.65 205000 2.1 1.3 2.8 not visible 2126.7 0.28 397000 2.6 0.0 5.7 not visible 22 56.3 0.60 365000 2.7 0.0 2.8not visible

What is claimed is:
 1. A slurry process for producing a copolymer of anisoolefin and at least one other comonomer comprising the step ofpolymerizing a reaction mixture comprising an isoolefin, a catalysthaving the formula AlY₃ wherein Y is a halogen and at least one of acycloconjugated multiolefin and an unconjugated cyclic olefin in thepresence of an activator selected from the group consisting of a carbocation producing species, a silica cation producing species and mixturesthereof.
 2. The process defined in claim 1, wherein the activator is acarbo cation producing species having the formula: R¹—x wherein R¹ is aC₁-C₄₀ hydrocarbon, optionally substituted with one or more heteroatoms,and X is selected from the group consisting of halogen, —OH and —OR²,wherein R² is the same or different as R¹ and is a C₁-C₄₀ hydrocarbon,optionally substituted with one or more heteroatoms.
 3. The processdefined in claim 2, wherein each of R¹ and R² is a C₁-C₄₀ straight chainor branched alkyl group, optionally having one or more unsaturations. 4.The process defined in claim 2, wherein each of R¹ and R² is asubstituted or unsubstituted C₅-C₄₀ aryl group.
 5. The process definedin claim 2, wherein each of R¹ and R² is a substituted or unsubstitutedC₃-C₄₀ cycloalkyl group.
 6. The process defined in claim 2, wherein X isselected from the group consisting of Cl, Br and I.
 7. The processdefined in claim 6, wherein X is Cl.
 8. The process defined in claim 2,wherein X is OH.
 9. The process defined in claim 2, wherein X is OCH₃.10. The process defined in claim 1, wherein the activator has theformula: X¹—R—X² wherein R is a C₁-C₄₀ hydrocarbon, optionallysubstituted with one or more heteroatoms, and X¹ and X² are the same ordifferent and each is a halogen, —OH or —OR³, wherein R³ is a C₁-C₄₀hydrocarbon, optionally substituted with one or more heteroatoms. 11.The process defined in claim 10, wherein R is a C₁-C₄₀ straight chain orbranched alkyl group, optionally having one or more unsaturations. 12.The process defined in claim 10, wherein R is substituted orunsubstituted C₅-C₄₀ aryl group.
 13. The process defined in claim 10,wherein R is a substituted or unsubstituted C₃-C₄₀ cycloalkyl group. 14.The process defined in claim 10, wherein R³ is a C₁-C₄₀ straight chainor branched alkyl group, optionally having one or more unsaturations.15. The process defined in claim 10, wherein R³ is substituted orunsubstituted C₅-C₄₀ aryl group.
 16. The process defined in claim 13,wherein R³ is a substituted or unsubstituted C₃-C₄₀ cycloalkyl group.17. The process defined in claim 10, wherein X¹ and X² are selected fromthe group consisting of Cl, Br and I.
 18. The process defined in claim17, wherein both X¹ and X² are Cl.
 19. The process defined in claim 1,wherein the activator comprises allyl chloride.
 20. The process definedin claim 1, wherein the activator comprises tert-butylchloride.
 21. Theprocess defined in claim 1, wherein the activator comprises:

wherein R is C₁-C₄₀ hydrocarbon, optionally substituted with one or moreheteroatoms.
 22. The process defined in claim 1, wherein the activatoris selected from the group consisting of:


23. The process defined in claim 1, wherein the activator is:


24. The process defined in claim 1, wherein the activator is selectedfrom the group consisting of cis and trans isomers of: CH₂C—CH═CH—CH₂Cl.25. The process defined in claim 1, wherein activator has the formula:


26. The process defined in claim 1, wherein the activator is a silicacation producing species having the formula: R⁴R⁵R⁶SiX wherein R⁴, R⁵and R⁶ are the same or difference and each is a C₁-C₄₀ hydrocarbon,optionally substituted with one or more heteroatoms and X is a halogen.27. The process defined in claim 26, wherein each of R⁴, R⁵ and R⁶ is aC₁-C₄₀ straight chain or branched alkyl group, optionally having one ormore unsaturations.
 28. The process defined in claim 26, wherein each ofR⁴, R⁵ and R⁶ is a substituted or unsubstituted C₅-C₄₀ aryl group. 29.The process defined in claim 26, wherein each of R⁴, R⁵ and R⁶ is asubstituted or unsubstituted C₃-C₄₀ cycloalkyl group.
 30. The processdefined in claim 26, wherein X is selected from the group consisting ofCl, Br and I.
 31. The process defined in claim 1, wherein the activatorcomprises trimethyl silyl chloride.
 32. The process defined in claim 1,wherein said isoolefin is selected from the group consisting ofisobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-penteneand mixtures thereof.
 33. The process defined in claim 1, wherein thecycloconjugated multiolefin is selected from the group consisting ofcyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,3-cyclohexadiene,1-methyl-1,3-cyclohexadiene, 1-methylene-2-cyclohexene,2-methyl-1,3-cyclohexadiene, 1,3-dimethyl-1,3-cyclohexadiene andmixtures thereof.
 34. The process defined in claim 1, wherein theunconjugated cyclic olefin comprises β-pinene.
 35. The process definedin claim 1, wherein the catalyst comprises AlCl₃.